Amino-coumarin- sulfonates



Reissued Sept. 1, 1953 Swiss firm No Drawing. Original No. 2,600,375,dated June 17, 1952, Serial No. 752,277, June 3, 1947. Application forreissue January 26, 1953, Serial 8 Claims.

In Switzerland June 14, 1946 Matter enclosed in heavy brackets I: jappears in the original patent but forms no part oi. this reissuespecification; matter printed in italics indicates the additions made byreissue.

According to this invention new water-soluble coumarin derivatives areobtained by introducing acid or ion-inactive (non-ionic) groups intocompounds of the general formula:

in which A represents an aromatic nucleus of which two vicinal carbonatoms form part of the unsaturated lactone ring, and which nucleus maycontain substituents, R and R1 represent hydrogen or an alkyl, aryl oraralkyl radical, which may contain substituents, and in which at leastone of the radicals A, R and R1 contains at least one amino group whichmay contain substituents.

The term acid groups denotes sulfonic acid, acid sulfuric acid ester orcarbo-xyl groups. As is known, ion-inactive or non-ionic groupsimparting Solubility in water form in water neither anions nor cations.Examples of such groups are polyglycol ether radicals which may beintroduced by the action of ethylene oxide, further polyglycerineradicals which may be introduced easily, for example, with glycid'e. Themost important groups among the ion-inactive atom' groupings impartingsolubility in water, however, are polyglycol ether radicals. The abovementioned acid and ion-inactivegroups imparting solubility in water mayalso be designated as groups imparting solubility in water which arefree from basic nitrogen atoms, such as are present, for example, inquaternary ammonium groups. Substituted amino groups are, for example,groups in which at least one hydrogen atom is replaced by hydrocarbonradicals, such as alkyl, aryl and aralkyl radicals, or further by acylradicals, for example, carboxylic acid radicals.

As is known, basic amino group contain at the nitrogen atom onlyhydrogen atoms or hydrocarbon radicals which may be substituted, but arefree from acyl radicals.

The compounds of the above formula and also their water-soluble saltsand derivatives do not possess the character of dyestufls, produce inaqueous solution a blue to violet fluorescence in ultra-violet light andhave a more or less pronounced affinity towards a very wide variety ofsubstrata. Owing to these properties the products of this invention aresuitable for improving materials, especially fibrous materials, whichproducts whn applied to the materials improve the whiteness or un'dy'edmaterials and the purity of color of dyed materials. In the case ofundy'ed, original-1y yellowish materials the improvement in whitenessbecomes apparent by the fact that the applied compound producing a blueto violet fluorescence imparts a white appearance to the originallyyellowish material.

As compounds of the above general formula which may be produced inaccordance with the present invention there may be mentioned, forexample, the following compounds, all of which are obtainable by theaction of a solubilizing agent capable of introducing a solubilizinggroup free from basic nitrogen atoms:

(A) Compounds of the formula wherein R and R1 have the significancegiven in the first paragraph of the specification,- and wherein A, R. orR1 contains the atom grouping u most-N- for example, products of theformula in which R, R1 and R3 have the meanings given above, by treatingit with an aldehyde-bisulfite or ketone-bisulfite compound, or with analdehyde or ketone and sulfur dioxide. In this formula the customarymanner of designating coumarins has been indicated. By treatment with aformaldehyde-bisulfite compound, for example, by heating the appropriateamino coumarin with an aqueous solution of sodium formaldehyde bisulfitea compound of the formula is obtained, in which R, R1 and R3 and Me havethe meanings given above. Instead of formaldehyde-bisulfite compoundsthere may be allowed to act in a similar manner bisulfite compounds ofother aldehydes, such as acetaldehyde, acrolein, benzaldehyde orfurfurol, or bisulfite compounds of etones, such as acetophenone.Especially valuable, however, are the water-soluble salts, obtainablewith formaldehyde bisulfite, of compounds of the formula wherein R andR1 have the meaning given above, and R2 stands for hydrogen or alkyl.

(B) Compounds of theabove mentioned general formula in which A, R or R1contains a sulfonic acid or sulfuric acid ester group. Such sulfonicacids are obtained by treating an appropriate amino coumarin compoundwith a suitable sulfonating agent which replaces a hydrogen atom by an-SO3I-I group, such as concentrated sulfuric acid, chloro-sulfonic acid,or sulfuric acid containing sulfur trioxide. Especially easy to prepareare sulfonic acids of amino coumarin of the formula in which R, R1 andR2 represent hydrogen or an alkyl, aryl or aralkyl radical. By treatingsuch benzylated amino coumarins with concentrated sulfuric acid, whichmay, if desired, contain ad- ,ditional sulfur trioxide, thecorresponding sulionic acids are obtained. In a similar manner aminocoumarins containing the atomic grouping 0-0 Fir-O or other aminocoumarins, such as 4-methyl-7- ethylamino-coumarin, may be sulfonated.

Amino coumarins which contain. as a substituent in the amino group analkyl or aralkyl radical containing a sulfonic acid group can also beobtained by treating an appropriate amino coumarin with a halogenatedalkyl sulfonic acid or a sulfonated aralkyl halide, which likep-bromethane sulfonic acid or benzyl chloride-parasulfonic acid containsa reactive halogen atom, if desired, in the presence of an acid-bindingagent. The above mentioned halogenated alkyl sulfonic acids orsulfonated aralkyl halides contain a halogen atom bound to an aliphaticchain.

When the amino coumarin used as starting material contains a tertiaryamino group a quaternary ammonium compound is formed by the action ofthe aforesaid halogen-sulfonic acid. Sulfuric acid esters can beobtained by treating with a sulfonating agent an amino coumarincontaining an hydroxyalkyl group, for example, an amino coumarin of thegeneral formula in which R, R1 and R2 have the meanings given above. TheN-hydroxy-ethylamino-coumarins used as starting materials are easilyobtained with the aid of ethylene oxide or ethylene chlorhydrin.

(0) Compounds of the above mentioned general formula HO-OHaOlIz-N inwhich A, R or R1 contains the group -1| l'SO9Me (R2=hydrogen, alkyl,aryl or aralkyl, and

Me=a cation). Such sulfamic acids can be obtained from co-umarins havingprimary or secondary amino groups, for example, by treatment With theaddition product of pyridine with sulfur trioxide, advantageously in thepresence of an excess of pyridine.

(D) Compounds of the above formula in which an amino group present in A,R or R1 contains as a substituent an alkyl or aralkyl radical containinga carboxyl group. Such carboxylic acids are obtainable by the reactionof an appropriate amino coumarin with an aliphatic halogen-carboxylicacid, such as chloracetic acid, uchloropropionic acid, u-bromosuccinicacid, or with an aralkyl halide containing in the aryl residue acarboxyl group, such as chloromethyl-benzoic acid orchloromethylsalicylic acid. In this reaction, which may be carried out,for example, at 60-100" (2., an acidbinding agent may be present.

which contains a primary amino group, in A, R or R1, with acarbonylcompound' which contains atleast one group imparting solubilityin water or an atomic grouping convertible into a group impartingsolubility in water. Examples of such carbonyl compounds are: Aldehydeor ketone sul ionic acids, such as, acetaldehyde, disulfonic acid,benzaldehyde disulfonic, acid 'oracetone sulfonic acid; aldehyde orketonecarboxylic acids, such as glyoxylic acid; and furthermorepolyoxy-aldehydes such as reducing sugars,. for example, l-arabinose,d-glucose, d-fructose or, maltose. As an example of a carbonyl'compoundcontaining an atomic grouping convertibleinto a group impartingsolubility in, waterv there may be mentioned crotonaldehyde, which,,after the condensation, can easily be additively combinedat the doublebond with-bisulfite, for. example. The condensation may becarried, out,for example, by heating the components,,for example, at 80-100 Cg, inthe presence of "a suitable solvent, for example, with the additionofamixtureof alcohol and glacial acetic, acid;

(F) Condensation, products of" an amino coumarin of the above mentioned;general formula which contains a primary or: secondary amino group in A,R or- R1, withanN-methylol-amide of a carboxylic acid containing atleast one group imparting solubility in water orwithamixture offormaldehyde and an amideof a-carboxylic acid of the aforesaid kind. TheN -methylol carboxylic acid amides or carboxylic acid amides may be de-'in which the amino: group present in A, R. or R1 contains at least onepolyglycol ether residue. Such products areeasily obtainable by theaction all) i as.

for example, productsyof theformula in which R, R1, R2, RsandRsrepresenthydrogen or an alkyl, aryl' or aralkyl radical, which may containsubstituents, and R4 represents an alkyl, aryl or aralkyl radical, whichmay contain substituents. Such products are easily obtainable from aminocoumarins having primary or secondary amino groups by condensation withmercapto-compounds in the presence of aldehydes or acetals thereof. As amercapto-compound there is advantageously used'thioglycollic acid.However, other mercaptans, for'example ;3-hydroxyethylmercaptan orthiosalicylic acid, may also be employed. There may be usedas aldehydesin the above mentioned condensation, for example, formaldehyde,acetaldehyde or benzaldehyde, and furthermore'aldehydes having a groupimparting solubility in water, such as glyoxylic acid, acetaldehydedisulfonic acid or a benzaldehyde sulfonic acid; The above mentionedcondensation is advantageously conducted at a raised temperature, forexample, 60-100 C., if desired, in the presence of a solvent such asmethanol, dioxane or glacial acetic acid; Acids which are capable ofacting as catalysts, such as acetic acid or hydrochloric acid, may beadded, when the solventused is not itself an acid. The individualstarting materials may be brought into reaction simultaneously. orinsu-ccession.

(I) Water-soluble salts of compounds of the formula wherein R and R1have. the significance given in,

for example, products of the formula in which R and R1 representhydrogen or an alkyl, aryl or aralkyl radical, which may containsubstituents, and

O\ CRzC HO/ represents the monovalent acyl residue of a dicarboxylicacid. Such amide-acids are easily amino coumarins corresponding to theformula wherein A is a radical of the benzene series in which twovicinal carbon atoms are members of the unsaturated lactone ring, R andR1 are members selected from the group consisting of hydrogen, alkyl,aryl and aralkyl, at least one of the radicals A, R. and R1 containing amember selected from the group consisting of primary amino groups,secondary amino groups, tertiary amino groups and acylated amino groups.

The improvement of the materials in accordance with the invention may becarried out by impregnating the material to be improved with y asolution, for example, an aqueous solution, or a.

dispersion of one of the compounds hereinbefore described, and, aftercentrifuging or squeezing the material, drying it. Derivatives ofproducts of the aforesaid general formula which contain acid groups areadvantageously applied in the form of aqueous solutions of their metalsalts. Besides the above mentioned aqueous solutions, there also comeinto consideration for use in the improving process of the inventionsolutions in organic solvents. It is also possible to treat materialswith the compounds of the general formula hereinbefore first mentionedin dispersed form, for example, with dispersions which are obtained bymeans of dispersing agents such as soaps, soap-like substances,polyglycol ethers of fatty alcohols, sulfite cellulose waste liquor orcondensation products of, if desired, alkylated, naphthalene sulfonicacids with formaldehyde.

The compounds of the present invention may also be applied in the courseof the manufacture of the material to be improved. In this case thecompound may be added, for example, to a paper mass or a viscosesolution which is to be used for making films or filaments, or toanother spinning mass, for example, to a spinning mass of a 8 linearsynthetic polyamide or an acetyl-cellulose spinning solution.

The products of the invention may also be added, for example, to liquorsused for imparting a crease resistant finish. They are also suitable forthe after-treatment of discharge prints.

In general small quantities of the products of the invention sufiice toproduce the improvement.

The compounds of this invention may also be used in admixture withauxiliary substances of the kind used for improving fibrous materials,for example, together with washing agents (for example, soaps salts ofsulfonated washing agents, such as salts of sulfonated benzimidazolescontaining as a substituent at the Z-carbon atom a higher alkyl radical,mono-carboxylic acid esters of 4-sulfophthalic acid with higher fattyalcohols, fatty alcohol sulfonates or condensation products of higherfatty acids with aliphatic hydroxyor aminosulfonic acids). In thismanner the material to be improved can be simultaneously washed andbleached. An especially pronounced brightening effect is produced whenundyed animal fibers, especially wool, are treated with mixturescontaining such washing agents.

As materials which can be improved with the products of the invention,there may be mentioned, for example, the following:

Nitrogenous natural or artificial materials such as wool, silk orsynthetic .polyamide fibers; also cellulose materials such as cellulose,paper or textile materials of cotton, linen or regenerated celluloseincluding regenerated cellulose staple fibers; and finally materialsproduced synthetically for example, by polymerization. However, the bestefiects are produced by the present process on animal fibers. Thematerial to be improved may be in any desired form, for example, infibrous form or in the form of film. Moreover, the material may, forexample, be undyed, dyed or printed. Metal surfaces which are pretreatedin a suitable manner, for example, anodically oxidized aluminiumsheeting, may also be treated in accordance with the invention.

The following examples illustrate the invention the parts being byweight unless otherwise stated, and the relationship of parts by weightto parts by volume being the same as that of the kilogram to the liter:

Example 1 A formaldehyde-bisulfite solution is prepared from 52 parts ofa sodium bisulfite solution of 40 per cent. strength and 16.2 parts ofan aqueous formaldehyde solution of 37 per cent. strength. 12 parts of4methyl-7-amino-coumarin are added and the whole is boiled in a refluxapparatusuntil all the 4-methyl-7amino-coumarin is dissolved, whichrequires 4-5 hours. The whole is allowed to cool, whereupon thecondensation product precipitates. Portions still remaining in solutioncan be precipitated by the addition of a salting-out agent, for example,a solution of sodium chloride. The whole is filtered, the residue iswashed if necessary with sodium chloride solution, and dried.

A bright powder is obtained, viz., the sodium salt of the acid of theformula '29 which is .soluble in water. Its solutions produce a.blue-violet fluorescence. Wool or .cotton which has been treated with anaqueous solution thereof has a greater whiteness *than' the untreatedma- .terial.

,- Ex ample :2

520 parts "of sodium bisulfite solution of 40 per cent. strengtharemixed with 162 parts of formaldehyde solution of '37 'per 'cent.strength, and '1 part of sodium carbonate and 60 parts of4=methyl'7-ethyl-amino-coumarin are added to the'mixture. "Ihe whole-ismaintainedat 115- 120 C. in a pressure vessel for'B-12-h'ours. It isthen allowed to cool, and, if desired, filtered to remove smallquantities of undissolved constituents, and the filtrate is evaporatedto dryness at 50-'70 C. under reduced pressure. When carrying outxthereaction atabout 100 C. it lasts considerably longer.

A slightly yellowish powder is obtained which can be freed from saltst'o a considerable extent by extraction with methanol. The new productof the formula .Cz'HB =is abright 'powderwhich'is soluble in water. Itssolutions produce a blue-violet fluorescence. Woolwhich has been treatedwith such a solution possesses greater whiteness than the untreatedwool.

Instead of formaldehyde there may also be used acetaldehyde .for theabove'described .reaction.

Example 3 A benzaldehyde-bisulflte solution .is prepared from 26 partsof a sodium bisulfite solution of 40 per cent strength, 10i6 parts ofbenzaldehyde :and 50 .parts of water, and the solution is renderedweakly'alkaline by theaddition of an aqueous solution of sodium:carbonate. 3 parts of *4-methyl-'l-aminocoumarin are added and the"Whole .is'boiled for 1 hour in 'a-refiux apparatus. .The resultingsolution is evaporated to dryness. water-.soluble bright powder of theformula "is obtained. Its *solutlons "produce a bluish fluo- "rescence.

4-methyl-7 arninomoumarin may be treated in asimilar manner withasolution'of cinn-amaldehyde-bisulfite or of -salicylaldehyde bisulfite,The water-soluble powders so obtained have properties similar to thoseof the eompoun'd'obtained with benzaldehyde.

Example 4 3.5 parts of 4-methyl-'l-amino-coumarin and 4.6 parts ofsodium benzyl chloride-4-sulfonate are boiledinBO parts of ethylalcohol. The hydrochloric acid formed is neutralized with a solutionof.1.3,par-ts of :sodiumcarbonate in 5 parts il of I water. in .such.manner that a veryweaklyacid reaction persists throughout. :After :about18 hours the whole is evaporatedto dryness asmall quantity of '4emethyl-7-amino-coumarin .still present is dissolvedout with .chlorobenzene,=andthe residue'is again dried.

A bright powder oftheformula is obtained which is solublednwater. Itssolutions produceabluishfluorescence.

Example 5 '17 parts of 4-.-methyl l7-'a;minoscoumarin, .35 parts ofsodium 'benzaldehyde2:4-dis1ilfonate, 500 parts of ethyl alcohol and 500parts of glacial aceticacidare boiled for .4 hours. The resultingsolution -is evaporated .to .dryness at 40-50 .C. under reducedpressure. Anyvsmal1- quantityof 4-methyl-7-amino-coumarin still presentmay be dissolved out with benzene.

A powder of theprobable'formula 'SOzNa is 'obtaine'd'which issolubleiinwater. .Its'solutions produce a bluish fluorescence.

'Example 6 9 parts of chloro'sul'foriic "acid followed by 4 parts of"4-'methyl=7-amin'o-coumarin are added 'to 50 parts'of ;pyridine"=ata'te'mperature below 40 C. The temperatureis'increased to "the'boilingpoint andthe whole-is maintained ava gentle boil until a test portion'becomes'soluble'in'Water, which requires "1-2 hours. The whole'is'then'allowed to cool, *poured' into water, neutralized with sodiumcarbonate, and the liquid is evaporated to dryness at-40-50cpunder'reduced pressure. The reaction product canbe freed "frominorganic salts to a considerable extent by extraction with methanol.The product is abrightpow der of the formula \(ll H -o='o NaOaS If whichdissolves in water to give ablue-v'iolet fluorescence.

Example '1 solved' in 30 parts of sulfuric acid monohydrate, and thewhole is stirred at 70-75 C. until a test portion is soluble in dilutesodium carbonate solution. The whole is then cooled, poured on to ice,neutralized with caustic soda solution, and evaporated to dryness at(SO-80 C. under reduced pressure. The powder so obtained is extractedwith hot methanol, and the extract solution is evaporated to dryness.

A bright powder of the formula o n i= NaOaS H O is obtained which issoluble in water. Its solutions produce a bluish fluorescence.

Example 8 4 parts of 4-methy1-7-(dimethylamino)-coumarin, 6 parts ofsodium benzyl chloride-parasulfonate and 40 parts of ethyl alcohol areboiled in a reflux apparatus for a few hours and then allowed to cool.The precipitated condensation product is removed by filtration, washedwith alcohol and dried. In order to remove a small quantity of4-methyl-7-(dimethylamino)-coumarin still present the powder so obtainedis digested with benzene, the solution is filtered, and the residue iswashed with benzene and dried.

A bright powder is obtained which is soluble in water. Its solutionsproduce a bluish fluorescence in ultraviolet light.

Example 9 4 parts of 4-methyl-7-(ethyl-benzylamino)- coumarin aredissolved at room temperature in 50 parts of sulfuric acid monohydrate.8 parts of fuming sulfuric acid containing 24 per cent of sulfurtrioxide are slowly added dropwise to the solution which is cooled to 0C. As soon as a test portion is soluble in dilute sodium carbonatesolution the sulfonation mixture is poured on to ice, neutralized withcaustic soda solution, evaporatedto dryness, and extracted with methanolto remove inorganic salts. The extract solution is then evaporated todryness.

A powder of the formula bluish fluorescence.

Example 10 6 parts of 4-methyl-7-amino-coumarin are maintained at thegentle boil with 50 parts of ethyl alcohol and 8 parts of the quaternaryaddition product of trimethylamine with methylol chloracetamide forhours. The alcohol is removed by distillation, the residue is treatedwith benzene in order to remove a small quantity of starting materialstill present, and dried. The resulting powder is, if necessary,dissolved in water, freed from small quantities of solid impurities byfiltration, and the filtrate is evaporated to dryness at a lowtemperature under reduced pressure. A bright powder s obtained I 12which is soluble'in water. a violet-blue fluorescence.

Example 11 3.5 parts of 4-methyl-7-amino-coumarin are added to asolutionof 3 parts of mono-chloracetic acid, 2.6 parts of sodiumcarbonate and 30 parts of water. The whole is stirred for 15 hours at70-90 C., allowed to cool, neutralized with dilute sulfuric acid, ifnecessary, filtered to remove unchanged starting material still present,and the filtrate is evaporated to dryness.

A bright powder of the formula Its solutions produce is obtained whichis soluble in water. Its solutions produce a violet-blue fluorescence.

Example 12 6 parts of 4-methyl-7-amino-coumarin are suspended in 70parts of dioxane at 70-80" C1, and then ethylene oxide is introduced.After about 4 hours the temperature is raised to 0., and ethylene oxideis introduced until a test portion in soluble in water. The reactionproduct, when freed from easily volatile constituents, is a brightpowder of the formula (ll-H H0-o112-o11,-(0-oH1-crm.]=N

0 which dissolves in water. Its solutions produce a violet-bluefluorescence.

Example 13 '7 parts of phenyl isocyanate dissolved in 7 parts ofchlorobenzene are introduced dropwise into a solution of 8.5 parts of4-methyl-7-aminocoumarin in 400 parts of chlorobenzene. The whole isthen heated at the boil for 1 hour and allowed to cool. The precipitatedcondensation product is separated by filtration, washed withchlorobenzene and benzene until it is free from a small quantity ofunchanged starting material, and then dried.

A powder is obtained which is insoluble in water.

1 part of the powder is dissolved in 10 parts of sulfuric acidmonohydrate at 05 C2, 5 parts of fuming sulfuric acid containing 24 percent of sulfur trioxide are then added dropwise. The whole is stirred at0-5 C. until a test portion is soluble in dilute sodium carbonatesolution, and then poured on to ice. The precipitated sulfonic acid isseparated by filtration, stirred with water, converted into its sodiumsalt by means of caustic soda solution, and the resulting solution isevaporated to dryness.

A bright powder of the formula i bt n d wh ch soluble in water. Itssolu- 1.13 tions produce a bluish-violet :ffiuorescence in ultravioletlight.

Water-soluble productsv having similar properties are obtained bysulfonating B-benzoyl aminocoumarin .or 3--- (para acetyl -amino phenyl)coumarin.

Example 14 Wool cloth is treated for /4 hour :at '40-5"0 TC. in a bathcontaining per'liter of water, 0.1 gram of14-methyl-'7-ethyl-amino-coumarin dissolvedin 50 grams of sulfuric acidof 2per .cent strength. The liquor ratio is 1:40. The material is :thenrinsed and dried.

"The wool has a greater whiteness thanthe'untreated material.

A similar efiect is obtained by using 4-methyl- 7-dimethylamino-coumarininstead of 4-rnethyl '7-ethyl-amino-coumarin.

Example .16

100 grams of wool are washed for /2 hour at 50-.5.5 C. in l liters.of.water which contain .0.16 gram of 4-methyl-7-dimethylamino-coumarindissolved in 32 grams of sulfuric acid of 2 per cent strength, and 8grams of the sodium salt of heptadecyl N benzyl-benzimidazole'disulfonic acid.

The washed wool has a whiter appearance than wool which'has been-washedwithout the addition of 4-methyl-7edimethylaminmcoumarin.

A similar result is obtained by .using, for example,4-methyl-7-ethylamino-coumarin, instead of4-methyl-7-'dimethylaminoecoumarin.

Example '17 Wool isw-ashed at-'40 50'C. .in a'bath icontaining, perliter, :1 gram :of :the .disodium.-.salt of .N- .benzyla-:heptadecyl-benzimidazole disulfonic acid, a small quantity of sodiumsulfate and:,0i.0 gram of the product obtained as described in Example2, rinsed and dried.

The wool .-so treated has a greater whiteness than material which hasbeen washed without the addition of the productof .Example 2.

Example 18 "Natural silk is treated at room temperature and a liquorratio of 1:40 in a bath which contains, per liter, Ol'gram of theproduct obtained as described .in .Example 1 and -1 gram of acetic acidof 40 per cent strength. The material is then rinsed and dried. .Thesilk has .a greater whiteness than the vuntreatedmaterial.

Example 19 .Natural'silk is treated at-a .liquor-ratio-of12.410 for V412 hour in a bath .heated ;at-40-45 which contains, per liter, 0.-05gramof e-methyl- '7-dimethylamino-coumarin-dissolved-in .12; gr-ams ofsulfuric acid of .2 .per centnstrength. Thematerial is then rinsed and.dried.

314 The :tsilkrhas vsh m-eater {whiteness .than :the untreated material.

Example Bleached cotton cloth-is'treated on the foulard with .a solutionwhich contains 0.4 gram of .the product obtained .as .described .inExample .2.

Thecotton clothhasa whiter appearance than the untreated material.

Example 121 Cottonyarnistreated 'at.a liquor ratio of 1:30 for about A;hour in .a bath which contains per liter, 0.1 gram o'f'the productobtained as described in Example A. After rinsing and drying the cottonyarn has a greater whiteness than the untreated .material.

Example 22 Cellulose .acetate artificial-silk is treated in a bathcontaining, .per liter, 0.025 gram of 4-methyl-71dimethyl'amino-conmarin.dissolved in .5 grams .o'fsulfuricacidoffzper cent. strength, and 1.5 grams of thecondensation product ofoleyl a1- cohol with about'..20.mo'1s of ethylene oxide. The liquorratio is 1:40. By this treatment the cellulose acetate artificial silkis considerably brightened.

.Assimilar .efiectis :obtained: by using, instead of the4=methyl-ledimethylaminocoumarin, 0.05 gram pf-A-.methyl-kethylamino-coumarin.

Example '23 :Synthetic polyamide ifibers, .for example, .such as areobtainable from hexamethylene diamine and adipic acid, are treated for/2 hour at -50 C. in a bath containing, per'liter, 0.2 gram of theproduct obtainableasdescrihedinExample 2 and .l. gram ;o fconcentrated.siil'furic acid. The fibers possess a Whiter-appearancethanthe untreated fibers.

Example 24 Upon a cotton fabric dyed with '3 per cent. of Direct ScarletWG (Schultz,'Farbstofftabellen, 7th ed, vol. II, page 88) is printed thefollowing color discharge.

"Grams Sodium .formaldehyde-sulfoxylate 150 Crystal .gum (1:2) 500Glycerine .50 Water 300 The printed-material is dried,.steamed, washedin running water, and again .dried.

The material sotreated is then after-treated at 20-25" C. and at aliquorratio'of 1:50 for 15 minutes in a .bath containing, per liter,lgram of the product obtained as described in Example 1.

In this manner the whiteness of the discharged parts is enhanced.

Example 25 To a paper pulp in a-hollander andcontaining :parts ofpaper,are first added 2 parts of resin size-and-after 15zminutes4-parts of theproduct obtained as'described .in .Example 1 dissolved in .80 ,parts-ofwater. .After afurther IS-minutes 3 partsof aluminium sulfate are added.The paper pulp so-:treated is then-passed by way of the mixing vat tothe paper-machine.

The papertreated-in this manner has-a greater whiteness-than theuntreated paper.

A similar .effect zis obtained by using instead of the product ofExample 1, 1 gram of the product obtainable as described in Example 2.

Example 26 0.01-0.1 per cent, (calculated on the acetyl cellulose) ofthe compound described in Example 1 and dissolved in methanol is addedto an acetylcellulose spinning solution containing about 25 per cent. ofacetyl cellulose. The fibers produced from the resulting spinningsolution possess a brighter appearance than those obtainable without theuse of the above addition.

Example 27 300 parts of a soap mass, containing, for example, 60 partsof fatty acid in the form of soap and 200 parts of water, are stirred at50 C. with 1 part of the product obtained as described in Example 1 anddissolved in a small quantity of water. After cooling, a soap isobtained which imparts to undyed textile materials in the usual Washingoperation a whiter appearance than is obtained by using the originalsoap alone.

Example 28 Anodically oxidized aluminium is treated at 40-80 C. for A,to hour in a bath containing 1 gram of the product obtained as describedin Example 1, and then dried.

The aluminum so treated exhibits a pronounced blue-violet fluoresence inultra-violet light.

Example 29 A solution of furfurol bisulfite is prepared from 65 parts ofa sodium bisulfite solution of 40 per cent. strength and 25 parts offurfurol. 0.5 part of sodium carbonate and '7 parts of 4-methyl-7-amino-coumarin are added. The whole is boiled in a reflux apparatusuntil the whole of the -methyl-'T-amino-coumarin has passed intosolution, and it is then filtered to remove small quantities ofimpurities and allow to cool. The crystal magma so obtained is dilutedwith sodium chloride solution of 10 per cent. strength, filtered, washedwith sodium chloride solution of 10 per cent. strength, and dried. Abright powder of the formula EH: i-i I no oo-N NaOaS H is obtained whichdissolves in water to give a blue-violet fluorescence.

Example 30 A solution of parts of 3-benzyl-4-methyl-7-ethyl-amino-coumarin in 50 parts of sulfuric acid monohydrate is allowedto stand for 1 hour. As soon as a test portion is soluble in water whichhas been rendered alkaline, the whole is poured on to ice-water, a smallquantity of sodium chloride is added to complete the precipitation, theprecipitated powder is separated by filtration, washed with sodiumchloride solution, stirred with water, neutralized with sodiumcarbonate, and the resulting solution is evaporated to dryness. Thesodium salt of sulfonated 3-benzyl- '16 4-methyl-7-ethylamino-coumarin,that is to say of the sulfonic acid of the formula is obtained in theform of a bright powder which is soluble in water.

Its aqueous solutions produce a sky blue fluorescence. By using insteadof 3-benzyl-4- methyl-7-ethyl-amino-coumarin, the benzylated aminocoumarins mentioned in Example 38 there are obtained water-solublecompounds having similar properties.

Example 31 5 parts of 4-methyl-7-ethylamino-coumarin are stirred with 50parts of chlorosulfonic acid at -95 C. until a test portion is solublein water which has been rendered alkaline. The whole is allowed to cool,poured on to ice, if necessary, filtered to remove small quantities ofstarting material, and the filtrate neutralized with an alkaline agent,for example, sodium carbonate, and evaporated to dryness on the waterbath. The powder of the formula so obtained is soluble in water. producea violet-blue fluorescence.

Example 32 3.5 parts of 4-methyl-7-aminocoumarin and 8 parts of sodium;8bromoethane sulfonate are boiled with 50 parts of ethyl alcohol. Thehydrobromic acid formed is neutralized with a solution of 1.3 parts ofsodium carbonate in 5 parts of water, and in such manner that a veryweakly acid reaction persists throughout. After boiling for 12 hours thewhole is diluted with 400 parts of water, neutralized with sulfuric acidof 10 per cent strength, and the solution is evaporated to dryness. Abright powder is obtained which can if necessary, be freed from startingmaterial by means of chlorobenzene. The powder of the formula Itssolutions is soluble in water to give a violet-blue fluorescence.

Example 33 8.7 parts of 4-methyl-'l-amino-coumarin are dissolved in 80parts of glacial acetic acid and 3.8 parts of formaldehyde solution of40 per cent strength by volume. 4.6 parts of thioglycollic acid areadded to the solution and the whole is heated for about 1 hour on thewater-bath. As soon as dissolution is complete the whole is allowed tocool, the precipitated powder is separated by filtration, theprecipitate is washed with glacial acetic acid and water, stirred withparts by volume of water, neutralized with an aqueous solution of sodiumcarbonate at 40-45 C .flltered tozremoved small quantities of solidconstituents, .and the solution is evaporated .to dryness at 5070 C.under reduced pressure.

The resulting powder, the sodium salt of the dissolves in water to givea violet fluorescence. Also the l methyl-'T-ethylamino-coumarin can bereacted in a similar manner with formaldehyde and thioglycol.

Example .34

4.8 parts of sodium glyoxyllate and 8.7 "parts of4-methyl-7-aminocoumarin are heated with 80 parts of glacial-acetic acidfor hour at 70 C. As soon as a test portion is soluble in water renderedalkaline with sodium carbonate, the solution is allowed to cool, theprecipitated powder is separated by filtration, stirred with 100 partsof I water. neutralized with sodium carbonate, fil- =tered,.and thefiltrateis evaporated .to dryness at 40-50 C. under reduced pressure.

.The resulting powder dissolves in water. Its solutions give a .bluishfluorescence in ultra-violet light.

Example .35

8.7 parts of 4-methyl-'l-amino-coumarin and "7.4 parts of phthalicanhydride are stirred with pressure.

A pale "yellowish powder of the formula (EH: v .1 i a 0:0 NaO o J N isobtained which is soluble in water. Its solutions produce a bluishfluorescence in ultraviolet light.

A product having similar properties is obtained by using instead ofphthalic anhydride an equimolecular quantity of maleic anhydride.

Example 36 parts of the powder obtained as described in Example 2are-worked up into a "fine-homogeneous powder with 40 parts of tartar"and parts of anhydrous sodium sulfate. It is soluble in water. Bytreating textile goods therewith they acquire a Whiter appearance thanthe untreated material. Instead of Glauber salt another anhydrousneutralsalt may be used.

The preparation "may also be prepared without the use of sodium sulfate.Furthermore, the quantities of the coumarin used and of the tartar maybe reduced or increased. Moreover, there may be used, instead of tartar,another solid acid 18 salt which yields a stable preparation with thecoumarin used above, for example, the "monosodium saltofphthalic acidorof oxalic acid.

Example ,3?

parts of a soap mass, containing, for example, 60 percent. of .fattyacid, are stirred with 0.1-3 parts .of 4-methyl-7-ethylamino-coumarin.When the mass solidifies a soap-like preparation is obtained. Textilegoods washed with this preparation possess a whiter appearance than amaterial which has been washed only with the soap itself.

For the purpose of more easy dispersion "the coumarin derivative may bepreviously dissolved in a small quantity of alcohol or another'solventmiscible with water, .and the :soap added to the solution in this form.It may also 'be first mixed with a liquid or molten free fatty acid, andthen Example 38 The procedure is the same as thatdescribed in Example3'7 except that instead of l-methyl- '7-ethylamino-coumarin, .use ismade of 0.1-3

parts of 3-benzyl-4-methyl'7sethyl-aminoecoumarin of the formula QEHENH\O/C=O which can be obtained from l-hydroxy-3-ethylaminobenzene anda-benzyl-acetoacetic acid ethyl ester by analogous processes.

It forms pale crystals which are insoluble in water. It dissolves inalcohol with a bluish fluorescence.

Instead of 3 benzyll-methyl-'l-ethylaminocoumarin the followingcoumarins may be used: '3 benzyl-4zfisdimethyl-'l-ethylamino-coumarin,3ebenzyl-4-methyl-'Z-amino-coumarin or3-benzyl-4-methyl-'7-dimethylamino-coumarin.

These coumarins can also be obtained from the corresponding phenols byanalogous processes.

Example 39 The sodium salt of 2-heptadecyl-N-benzylbenzimidazoledisulfonic acid is mixed with 01-3 per cent. .of finely pulverizedrl-methyl-T-ethylamino-coumarin. The powder .so obtained has a whiterappearance than one not containing l-methyl-Y-ethylamino-coumarin.Undyed textile goods which have been washed in the usual manner with'theresulting mixture, have a greater whiteness than material which hasbeen treated with the aforesaidsodium salt alone.

Instead of the above mentioned sodium salt, there may be used an alkalisalt of a sulfonic acid :of another benzimidazole, which contains ahigher-alkyl radical, or mixtures of .such alkali salts of sulfonatedbenzimidazoles which contain alkyl residues having chains of variouslengths. Furthermore, other coumarins may be used which contain in the7-position an amino group which may be alkylated or aralkylated. Therecome into consideration also mixtures with other synthetic washingagents, for example fatty alcohol sulfonates or condensation products ofhigher fatty acids with aliphatic hydroxyor amino-sulfonic acids. Also,mixtures of the aforesaid coumarins may be added to synthetic washingagents.

Example 40 1 part of 4 methyl '7 ethylamino-coumarin and 0.01 part ofa-[benzimidazyl-(2)l-fl-[N- methylbenzimidazyl-(2)l-ethylene dissolvedin alcohol are added to a solution of 100 parts of soap in 200 parts ofwater at lo-75 C. The alcohol is removed by distillation, and theresidue is allowed to cool while stirring. A soap-like preparation isobtained. Textile goods washed with this preparation exhibit a whiterappearance than materials which have been washed with soap alone. Thequantity of the optical bleaching agent used above may be decreased orincreased.

Example 41 The procedure is the same as that described in Example 40,except that, instead of a- [benzimidazyl (2) a [N methylbenzirnidazyl-(2)l-ethylene, there is used aZfi-dl- [N-methylbenzimidazyl-(Z)]ethylene or a mixture of both ethylenes or also other diimidazoles, forexample, those described in French Patent No. 908,852 or U. S. PatentApplication Serial No. 630,118, filed November 21, 1945, now U. S.Patent No. 2,488,289 dated Nov. 15, 1945.

Example 42 1-5 parts of the powder prepared as described in Example 36are covered with 1000 parts of water at 40-50 C., and wool is treatedwith the solution for about 20 minutes, rinsed and dried.

After this treatment the wool has a greater whiteness.

Example 43 Bleached cloth of regenerated cellulose staple fibers istreated on the foulard with a liquor which contains, in addition to theusual products required for producing an anti-creasing effect, 2.5 gramsper liter of the condensation product obtained as described in Example2.

After Working up the material in the usual manner, this treatmentproduces besides the anticreasing effect a pronounced brightening of thematerial.

When using, instead of the condensation product obtained according toExample 2, the sodium salt of the sulfonated3-benzy1-4-methyl-'7-ethylamino-coumarin, a similar effect is obtained.

Example 44 3 parts of 3-(para-acetylamino-phenyl) -coumarin are mixed atl-20 C. with 30 parts of sulfuric acid monohydrate. 12 parts of fumingsulfuric acid containing 24 per cent of sulfur trioxide are added indrops, the temperature being allowed to rise to 22 C. As soon as a testportion is soluble in dilute sodium carbonate solution, the mixture ispoured onto ice, sodium chloride solution is added for the completeseparation, the separated sulfonic acid is then filtered, stirred withwater, converted into the sodium salt with caustic soda solution, andthe solution is then evaporated to dryness. A bright powder is obtainedwhich is soluble in water. The solution produces a bluish fluorescencein the ultra-violet light. Example 15 parts of fuming sulfuric acidcontaining 24 per cent of sulfur trioxide are added at 15-20 C. to 5parts of fi-benzoylamino-coumarin and parts of sulfuric acidmonohydrate. As soon as a test portion is soluble in dilute sodiumcarbonate solution, the whole is poured onto ice, the separated sulfonicacid is filtered, stirred with water, converted into the sodium saltwith caustic soda solution and the solution is evaporated to dryness.

What I claim is:

1. A water-soluble amino coumarin derivative which forms an aqueoussolution showing fluorescence in ultraviolet light and corresponds tothe formula wherein each of R and R1 is a member selected from the groupconsisting of hydrogen, alkyl, aryl and aralkyl, R2 is a member selectedfrom the group consisting of hydrogen and alkyl, R3 is a member selectedfrom the group consisting of hydrogen, alkyl, aryl and furfuryl, and Meis an alkali metal.

2. A water-soluble amino coumarin derivative which forms an aqueoussolution showing fluorescence in ultraviolet light and corresponds tothe formula wherein each of R and R1 is a member selected from the groupconsisting of hydrogen, alkyl, aryl and aralkyl, R2 is a member selectedfrom the group consisting of hydrogen and alkyl, R3 is a member selectedfrom the group consisting of hydrogen, alkyl, aryl and furfuryl, and Meis an alkali metal.

3. A water-soluble amino coumarin derivative which forms an aqueoussolution showing fluorescence in ultraviolet light and corresponds tothe formula LITE; o

CzHs

4. A Water-soluble amino coumarin derivative wh1ch forms an aqueoussolution showing fluorescence in ultraviolet light and corresponds tothe formula 21 5. A water-soluble amino coumarin derivative which formsan aqueous solution showing fluorescence in ultraviolet light andcorresponds to the formula 6. A water soluble aminocoumarin derivativewhich forms and aqueous solution showing fluorescence in ultravioletlight and corresponds to wherein each of R and R1 is a member selectedfrom the group consisting of hydrogen, alkyl, aryl and aralkyl, R2 is amember selected from the group consisting of hydrogen and alhyl, R3 is amember selected from the group consisting of hydrogen, alkyl, aryl andjurfuryl, Me is an alkali metal and a: is or 1, R3 being hudrogen when:n is 1.

7. A water soluble aminocoumarin derivative which forms an aqueoussolution showing fluorescence in ultraviolet light and corresponds tothe formula R I C wherein each of R and R1 is a member selected from thegroup consisting of hydrogen, alkyl, aryl and aralkyl, R2 is a memberselected from the group consisting of hydrogen and alkyl, and A is alower alkyl-group containing as sole substitutent and SO3Me group.

8. A water soluble aminoooumarin derivative which forms an aqueoussolution showing fluorescence in ultraviolet light and corresponds tothe formula (IJH: c

C|H NaO;S-OH.CH;HN O

FRANZ ACKERMANN.

References Cited in the file of this patent or the original patenltUNITED STATES PATENTS Number Name Date 2,333,329 Miglarese Nov. 2, 19432,334,348 Miglarese Nov. 16, 1943 OTHER REFERENCES Bleaching,DyeingFibres, 2nd

ed., 1946, pp. 471-2.

